Hair compositions for damage treatment

ABSTRACT

A method of protecting the internal protein of hair from damage by ultraviolet light, comprising the step of applying, to the hair, a hair treatment composition comprising a lactone, a disaccharide, an inorganic salt and an organic acid or salt thereof, having a pH in the range of from 3 to 6.5 prior to the application of an ultraviolet light to the hair, and a use of such a hair treatment composition, in the treatment of hair, to protect hair from damage by ultraviolet light.

FIELD OF THE INVENTION

The invention relates to a method of protecting hair, preferably theinternal protein of hair, from damage by use of a hair treatmentcomposition comprising a lactone, a disaccharide, an inorganic salt andan organic acid or salt thereof, prior to the application of ultravioletdamage to the hair; and to a use of such hair treatment compositions inthe protection of hair from damage caused by ultraviolet light.

BACKGROUND AND PRIOR ART

Consumers regularly subject their hair to intensive treatment and careand styling routines to help them achieve their desired look. Theactions performed by consumers introduce modifications to the chemistryof hair keratin protein, which results in micro- and macro-structuralchanges which, in turn, change physical properties of the fibre: theconsequences of these changes are generally perceived by the consumer asdamage. Daily exposure to environmental elements exacerbates theproblem. Ultraviolet light is a particularly damaging environmentalelement, and is a particular problem in countries with a high UV index.

Hair that has been damaged has internal protein with a reduceddenaturation temperature compared to that of virgin hair. The reductionin denaturation temperature is attributed to a photochemical induceddegradation of the internal hair cortex proteins. The amino acids withinthe proteins absorb the UVA and UVB radiation producing free radicalsand breaks bonds, reducing the overall structural integrity of theinternal cortex proteins.

Various organic molecules and combinations thereof have been suggestedfor use in the treatment of damaged hair.

WO 2004054526 describes hair treatment compositions for the care andrepair of damaged hair, and for improving hair manageability, comprisinga disaccharide, (in particular trehalose).

WO 2004054525 describes hair treatment compositions for the care andrepair of damaged hair, and for improving hair manageability, comprisinga disaccharide (in particular trehalose), and a diol (in particular3-methyl-1,3-butanediol).

WO 2009040240 discloses hair treatment compositions comprising a lactoneand a disaccharide for the treatment of dry, damaged and/or unmanageablehair.

Our as yet unpublished European patent application, EP15169037.7,discloses the use of a hair treatment composition comprising a lactone,a disaccharide, an inorganic salt and an organic acid or salt thereof,having a pH in the range of from 3 to 6.5, in the treatment of hair, toincrease the denaturation temperature of the internal protein of hair.

Various low molecular weight compounds have also been used to protecthair from the damaging effects of chemical treatments.

Protein hydrolysates have been used to protect the hair from chemicaltreatments. For example, Roddick-Lanzilotta et al. have used apre-treatment with a protein hydrolysate to reduce the oxidative damageproduced by oxidative treatments (permanent colourants and bleaches).The inventors argue that the proteins act as sacrificial molecules,diverting the oxidative damage away from hair proteins(Roddick-Lanzilotta et al., J. Cosmet. Sci. 58 (July/August), 405-411(2007))

Anti-oxidants have also been used to protect hair from free-radicaldamage. For example, Meinert et al have investigated the use ofcommercially available antioxidants on sun protection properties of haircare products (Meinert et al., J Cosmet Sci. 55 Suppl:S105-12 (2004)).

Despite the prior art, there remains a need for better protection ofhair from ultraviolet light damage. Protection is distinct from repairin that it helps to prevent damage from occurring. Repair is requiredfor hair that is already damaged and repair treatments are typicallyapplied to hair after the hair has suffered damage, such as exposure toa damaging substance or action. In contrast, protection is requiredbefore the hair is damaged, thus reducing or preventing damage fromoccurring to the hair. Thus, the impact of the damage, such as exposureto a damaging substance or action is reduced.

The changes in hair that occur when the hair is damaged differsaccording to the type of damage. Heat damage caused by hair dryers andheated appliances such as tongs and straighteners is limited largely tothe cuticle of the hair. Likewise, combing and other mechanical damagemainly affects the cuticle with the internal proteins being minimallyaffected. Chemical treatments, for example bleach and colourants involvethe application of liquid actives to the hair whereas photochemicalsources, such as ultraviolet light, act on hair by radiation. Bothchemical and photochemical damage may reach the internal structure ofthe hair shaft.

The specific action of UV light on hair has been studied. For example,Coll. Antropol. 32 (2008) Suppl. 2: 163-165 Review; UV Damage of theHair; K Šebetić et al discloses that photochemical impairment of thehair includes degradation and loss of hair proteins as well asdegradation of hair pigment. UVB radiation is responsible for hairprotein loss and UVA radiation for colour changes. Absorption ofradiation in photosensitive amino acids of the hair and theirphotochemical degradation produces free radicals, which have an adverseimpact on hair proteins, especially keratin. Amino acids cystine,methionine, tryptophan, tyrosine and histidine are the most submissiveto photochemical degradation. It is further disclosed that protectingthe cuticle is very important for keeping hair shaft's integrity andthat this can be achieved by avoiding noxious impacts or byimplementation of hair care products with UV filters. Physical andchemical filters achieve protection from UVA and UVB radiation.

It is known from Robbins C. R. (2012) Chemical and Physical Behaviour ofHuman Hair that carbonyl groups are formed during oxidation at thepeptide backbone carbon during ultraviolet exposure. These carbonylgroups react with protein amino groups, primarily lysine. Thephotochemical breakdown of disulfide bridges occurs within theexocuticle and matrix of the cortex.

Oxidation of amino acids due to bleaching damage has been studied byDyer J M, Bell F, Koehn H, Vernon J A, Cornellison C D, Clerens S, etal. in Redox proteomic evaluation of bleaching and alkali damage inhuman hair. Int J Cosm Sci. 2013; 35(6):555-61. Epub 22 Jul. 2013. Aminoacids, such as serine, cysteine and phenylalanine, are seen to undergo aseries of structural changes, becoming rich in hydroxy, nitro andsulphoxy groups, as the level of bleach damage increases.

We also have found that different types of damage affect different aminoacids in the hair.

In a comparison between bleaching damage and UV damage we found thatmethionine is affected significantly more by UV than by bleachingdamage. On the other hand, bleaching leads to much higher levels ofaspartic acid leaching that UV light.

The difference in amino acids affected reflects the different modes ofaction for each type of damage.

We have now found that hair can be protected from damage by ultravioletlight by the application of a hair treatment composition comprising alactone, a disaccharide, an inorganic salt and an organic acid or saltthereof, which has a pH in the range of from 3 to 6.5, prior to theapplication of UV light to the hair.

The benefit is seen for hair that has previously been damaged, as wellas virgin hair.

Definition of the Invention

In a first aspect, there is provided a method of protecting hair fromdamage, comprising the step of applying, to the hair, a hair treatmentcomposition comprising a lactone, a disaccharide, an inorganic salt andan organic acid or salt thereof, having a pH in the range of from 3 to6.5, prior to the application of an ultraviolet light damage insult tothe hair.

In a second aspect of the invention, there is provided a use of a hairtreatment composition comprising a lactone, a disaccharide, an inorganicsalt and an organic acid or salt thereof, having a pH in the range offrom 3 to 6.5, in the treatment of hair, to protect hair from damage byultraviolet light.

Hair damage can be measured in many different ways. This inventionfocusses on the protection of the structural integrity of hair cortexproteins, as can be determined by Differential Scanning Calorimetry,single-fibre mechanical testing and numerous other methods. Theprotection of the first and second aspects is to the protein of thehair, preferably the internal cortex protein of hair.

The composition for use in the invention is preferably applied to thehair multiple times, to give a progressive increase in protection of theprotein.

In the method of the invention, the step of applying, to the hair, ahair treatment composition comprising a lactone, a disaccharide, aninorganic salt and an organic acid or salt thereof, having a pH in therange of from 3 to 6.5, is performed multiple times, preferably from 2to 50 times, more preferably from 5 to 30 times.

The Hair

The hair can be virgin hair or damaged hair.

The damage is caused by exposure of the hair to ultraviolet light,preferably the hair is exposed to ultraviolet light multiple times.

GENERAL DESCRIPTION OF THE INVENTION

Lactones

The composition for use in the invention comprises a lactone. Examplesof suitable lactones include:

(a) Aldonic Acid Lactones

Aldonic acids are polyhydroxy acids resulting from oxidation of thealdehyde group of an aldose to a carboxylic acid group, and the acid ofwhich can be represented by the following general formula:

R(CHOH)_(n)CH(OH)COOH

where R is H or an alkyl group (usually H) and n is an integer from 1 to6.

The aldonic acids form intramolecular lactones by removing one mole ofwater between the carboxyl group and one hydroxyl group.

The following are representative aldonic acid lactones:

-   2,3-dihydroxypropanoic acid lactones (glyceric acid lactone);-   2,3,4-trihydroxybutanoic acid lactones (stereoisomers:    erythronolactone, threonolactone);-   2,3,4,5-tetrahydroxypentanoic acid lactones (stereoisomers:    ribonolactone, arabinolactone, xylonolactone, lyxonolactone);-   2,3,4,5,6-pentahydroxyhexanoic acid lactones (stereoisomers:    allonolactone, altronolactone, gluconolactone, mannolactone,    gulonolactone, idonolactone, galactonolactone, talonolactone), and-   2,3,4,5,6,7-hexahydroxyheptanoic acid lactones (stereoisomers:    alloheptonolactone, altroheptonolactone, glucoheptonolactone,    mannoheptonolactone, guloheptonolactone, idoheptonolactone,    galactoheptonolactone, taloheptonolactone).

(b) Aldaric Acid Lactones

Aldaric acids are polyhydroxy dicarboxylic acids derived from an aldoseby oxidation of both terminal carbon atoms to carboxyl groups, and theacid of which can be represented by the following general formula:

HOOC(CHOH)_(n)CH(OH)COOH

where n is an integer from 1 to 4.

The aldaric acids form intramolecular lactones by removing one mole ofwater between one carboxyl group and one hydroxyl group.

The following are representative aldaric acid lactones:

-   2,3-dihydroxybutane-1,4-dioic acid lactones-   2,3,4-trihydroxypentane-1,5-dioic acid lactoness (stereoisomers:    ribarolactone, arabarolactone, xylarolactone, lyxarolactone);-   2,3,4,5-tetrahydroxyhexane-1,6-dioic acid lactones (allarolactone,    altrarolactone, glucarolactone, mannarolactone, gularic acid and    gularolactone, idarolactone, galactarolactone, talarolactone);-   2,3,4,5,6-pentahydroxyheptane-1,7-dioic acid lactones    (stereoisomers: alloheptarolactone, altroheptarolactone,    glucoheptarolactone, mannoheptarolactone, guloheptarolactone,    idoheptarolactone, galactoheptarolactone, taloheptarolactone).

(c) Alduronic Acids

Alduronic acids are polyhydroxy acids resulting from oxidation of thealcohol group of an aldose to a carboxylic acid group, and can berepresented by the following general formula:

HOOC(CHOH)_(n)CH(OH)CHO

where n is an integer from 1 to 4.

Many alduronic acids form intramolecular lactones by removing one moleof water between the carboxyl group and one hydroxyl group.

The following are representative alduronic acid lactones:

riburonolactone; araburonolactone; xyluronolactone; lyxuronolactone;alluronolactone; altruronolactone; glucuronolactone; mannuronolactone;guluronolactone; iduronolactone; galacturonolactone; taluronolactone;allohepturonolactone; altrohepturonolactone; glucohepturonolactone;mannohepturonolactone; gulohepturonolactone; idohepturonolactone;galactohepturonolactone and talohepturonolactone.

(d) Aldobionic Acids

Aldobionic acids are also known as bionic acids, and typically includeone monosaccharide chemically linked through an ether bond to an aldonicacid. Aldobionic acids may also be described as an oxidised form of adisaccharide or dimeric carbohydrate, such as lactobionic acid fromlactose.

In most aldobionic acids, the carbon at position one of themonosaccharide is chemically linked to a hydroxyl group at a differentposition of the aldonic acid. Therefore, different aldobionic acids orstereoisomers can be formed from two identical monosaccharides andaldonic acids respectively.

As with acids (a) to (c) above, aldobionic acids have multiple hydroxylgroups attached to carbon chains.

Aldobionic acids can be represented by the following general formula:

H(CHOH)_(m)(CHOR)(CHOH)_(n)COOH

where m and n are integers independently from 0 to 7 and R is amonosaccharide.

Aldobionic acids can form intramolecular lactones by removing one moleof water between the carboxyl group and one hydroxyl group.

The following are representative aldobionic acid lactones:

lactobionolactone; and isolactobionolactone;

maltobionolactone; isomaltobionic acid isomaltobionolactone;

cellobionolactone; gentiobionolactone; kojibionolactone;laminaribionolactone;

melibionolactone; nigerobionolactone; rutinobionolactone, andsophorobionolactone.

Preferably, the lactone is a delta lactone. More preferably the lactoneis selected from gluconolactone, galactonolactone, glucuronolactone,galacturonolactone, gulonolactone, ribonolactone, saccharic acidlactone, pantoyllactone, glucoheptonolactone, mannonolactone, andgalactoheptonolactone, most preferably the lactone is gluconaolactone.

Mixtures of any of the above-described carbohydrate-derived acids mayalso be used in the composition for use in the invention.

The total amount of lactone in hair treatment compositions for use inthe invention generally ranges from 0.02 to 20%, preferably from 0.05 to2%, more preferably from 0.05 to 0.8% by total weight lactone based onthe total weight of the composition.

Preferably, the total level of glucanolactone, trehalose and sodiumsulphate is from 0.005 to 5 wt %, more preferably 0.2 to 5 wt % by totalweight of the composition. Where the composition for use in the presentinvention is a shampoo, the preferred level is from 0.005 to 4 wt %,more preferably from 0.6 to 4 wt %, by total weight of the shampoo.Where the composition is a conditioner, the preferred level is from0.005 to 3 wt %, more preferably from 0.2 to 3 wt %, by total weight ofthe conditioner.

The Organic Acid

The composition for use in the present invention comprises an organicacid or its salt. Preferably the acid is a hydroxy acid, most preferablyan alpha hydroxy acid. Sutiable examples include glycolic acid, lacticacid, citric acid, mandelic acid and mixtures thereof. Suitable betahydroxy acids include propanoic acid, beta hydroxypropionic acid,betahydroxybutyric acid, salicylic acid, carnitine and mixtures thereof.Also suitable is sodium benzoate. Preferably, the acid is used at levelsof from 0.01 to 1 wt %, more preferably 0.1 to 0.75 wt %.

The Disaccharide

The present invention comprises a disaccharide, preferably thedisaccharide comprises of pentose or hexose sugars, more preferably thedisaccharide comprises of two hexose units.

Disaccharides can be either reducing or non-reducing sugars.Non-reducing sugars are preferred.

The D(+) form of the disaccharides are preferred. Particularly preferredare trehalose and cellobiose or mixtures thereof. Trehalose is the mostpreferred disaccharide.

The level of disaccharides present in the total formulation from 0.001to 8 wt % of the total composition, preferably from 0.005 wt % to 5 wt%, more preferably from 0.01 to 3 wt %, most preferably from 0.05 wt %to 2 wt %.

Inorganic Salt

Preferably, the composition according to the invention comprisesinorganic salt.

Examples of suitable inorganic salts include sodium sulphate, potassiumfluoride, calcium chloride, sodium chloride and potassium phosphate.

In one preferred embodiment the inorganic salt is an alkali metal salt,preferably the alkali metal salt is a sulphate, more preferably it issodium sulphate.

The alkali metal salt is present at a level from 0.001 wt % of the totalcomposition, preferably from 0.05 wt %, most preferably from 0.1 wt %.The maximum level of salt is less than 10 wt %, preferably less than 7wt %, more preferably less than 5 wt %.

In a second alternatively preferred embodiment the inorganic salt is asource of ammonium ions, preferably this is ammonium carbonate.

This second preferred inorganic salt is preferably present at a levelfrom 0.01 wt % of the total composition, more preferably from 0.05 wt %.The maximum level of ammonium carbonate is preferably less than 10 wt %,more preferably less than 5 wt %, most preferably less than 1 wt %. Itis further preferred if the level of ammonium carbonate is from 0.01 to2.0 wt % of the total composition.

The Hair Treatment Composition

Hair treatment compositions according to the invention may suitably takethe form of shampoos, conditioners, sprays, mousses, gels, waxes orlotions.

Preferably, the hair treatment composition is a rinse off hair treatmentcomposition, preferably selected from a shampoo, a conditioner and amask. More preferably, the shampoo and the conditioner are used oneafter the other, and most preferably used repeatedly over several washesor treatments.

Shampoos

Shampoo compositions for use in the invention are generally aqueous,i.e. they have water or an aqueous solution or a lyotropic liquidcrystalline phase as their major component.

Suitably, the shampoo composition will comprise from 50 to 98%,preferably from 60 to 90% water by weight based on the total weight ofthe composition.

Shampoo compositions according to the invention will generally compriseone or more anionic cleansing surfactants which are cosmeticallyacceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkylsulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoylisethionates, alkyl succinates, alkyl sulphosuccinates, alkyl ethersulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl etherphosphates, and alkyl ether carboxylic acids and salts thereof,especially their sodium, magnesium, ammonium and mono-, di- andtriethanolamine salts. The alkyl and acyl groups generally contain from8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated.The alkyl ether sulphates, alkyl ether sulphosuccinates, alkyl etherphosphates and alkyl ether carboxylic acids and salts thereof maycontain from 1 to 20 ethylene oxide or propylene oxide units permolecule.

Typical anionic cleansing surfactants for use in shampoo compositionsfor use in the invention include sodium oleyl succinate, ammonium laurylsulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate,sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammoniumlauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolaminedodecylbenzene sulphonate, sodium cocoyl isethionate, sodium laurylisethionate, lauryl ether carboxylic acid and sodium N-laurylsarcosinate.

Preferred anionic cleansing surfactants are sodium lauryl sulphate,sodium lauryl ether sulphate (n)EO, (where n is from 1 to 3), sodiumlauryl ether sulphosuccinate(n)EO, (where n is from 1 to 3), ammoniumlauryl sulphate, ammonium lauryl ether sulphate(n)EO, (where n is from 1to 3), sodium cocoyl isethionate and lauryl ether carboxylic acid (n) EO(where n is from 10 to 20).

Mixtures of any of the foregoing anionic cleansing surfactants may alsobe suitable.

The total amount of anionic cleansing surfactant in shampoo compositionsfor use in the invention generally ranges from 0.5 to 45%, preferablyfrom 1.5 to 35%, more preferably from 5 to 20% by total weight anioniccleansing surfactant based on the total weight of the composition.

Optionally, a shampoo composition for use in the invention may containfurther ingredients as described below to enhance performance and/orconsumer acceptability.

The composition can include co-surfactants, to help impart aesthetic,physical or cleansing properties to the composition.

An example of a co-surfactant is a nonionic surfactant, which can beincluded in an amount ranging from 0.5 to 8%, preferably from 2 to 5% byweight based on the total weight of the composition.

For example, representative nonionic surfactants that can be included inshampoo compositions for use in the invention include condensationproducts of aliphatic (C₈-C₁₈) primary or secondary linear or branchedchain alcohols or phenols with alkylene oxides, usually ethylene oxideand generally having from 6 to 30 ethylene oxide groups.

Other representative nonionic surfactants include mono- or di-alkylalkanolamides. Examples include coco mono- or di-ethanolamide and cocomono-isopropanolamide. Further nonionic surfactants which can beincluded in shampoo compositions for use in the invention are the alkylpolyglycosides (APGs). Typically, the APG is one which comprises analkyl group connected (optionally via a bridging group) to a block ofone or more glycosyl groups. Preferred APGs are defined by the followingformula:

RO-(G)_(n)

wherein R is a branched or straight chain alkyl group which may besaturated or unsaturated and G is a saccharide group.

R may represent a mean alkyl chain length of from about C₅ to about C₂₀.Preferably R represents a mean alkyl chain length of from about C₈ toabout C₁₂. Most preferably the value of R lies between about 9.5 andabout 10.5. G may be selected from C₅ or C₆ monosaccharide residues, andis preferably a glucoside. G may be selected from the group comprisingglucose, xylose, lactose, fructose, mannose and derivatives thereof.Preferably G is glucose.

The degree of polymerisation, n, may have a value of from about 1 toabout 10 or more. Preferably, the value of n lies from about 1.1 toabout 2. Most preferably the value of n lies from about 1.3 to about1.5.

Suitable alkyl polyglycosides for use in the invention are commerciallyavailable and include for example those materials identified as: OramixNS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.

Other sugar-derived nonionic surfactants which can be included incompositions for use in the invention include the C₁₀-C₁₈ N-alkyl(01-06) polyhydroxy fatty acid amides, such as the C₁₂-C₁₈ N-methylglucamides, as described for example in WO 92 06154 and U.S. Pat. No.5,194,639, and the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀-C₁₈ N-(3-methoxypropyl) glucamide.

A preferred example of a co-surfactant is an amphoteric or zwitterionicsurfactant, which can be included in an amount ranging from 0.5 to about8%, preferably from 1 to 4% by weight based on the total weight of thecomposition.

Examples of amphoteric or zwitterionic surfactants include alkyl amineoxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines(sultaines), alkyl glycinates, alkyl carboxyglycinates, alkylamphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkylamidopropyl hydroxysultaines, acyl taurates and acyl glutamates, whereinthe alkyl and acyl groups have from 8 to 19 carbon atoms. Typicalamphoteric and zwitterionic surfactants for use in shampoos for use inthe invention include lauryl amine oxide, cocodimethyl sulphopropylbetaine, lauryl betaine, cocamidopropyl betaine and sodiumcocoamphoacetate.

A particularly preferred amphoteric or zwitterionic surfactant iscocamidopropyl betaine.

Mixtures of any of the foregoing amphoteric or zwitterionic surfactantsmay also be suitable. Preferred mixtures are those of cocamidopropylbetaine with further amphoteric or zwitterionic surfactants as describedabove. A preferred further amphoteric or zwitterionic surfactant issodium cocoamphoacetate.

The total amount of surfactant (including any co-surfactant, and/or anyemulsifier) in a shampoo composition for use in the invention isgenerally from 1 to 50%, preferably from 2 to 40%, more preferably from10 to 25% by total weight surfactant based on the total weight of thecomposition.

Cationic polymers are preferred ingredients in a shampoo composition foruse in the invention for enhancing conditioning performance.

Suitable cationic polymers may be homopolymers which are cationicallysubstituted or may be formed from two or more types of monomers. Theweight average (M_(w)) molecular weight of the polymers will generallybe between 100 000 and 2 million daltons. The polymers will havecationic nitrogen containing groups such as quaternary ammonium orprotonated amino groups, or a mixture thereof. If the molecular weightof the polymer is too low, then the conditioning effect is poor. If toohigh, then there may be problems of high extensional viscosity leadingto stringiness of the composition when it is poured.

The cationic nitrogen-containing group will generally be present as asubstituent on a fraction of the total monomer units of the cationicpolymer. Thus when the polymer is not a homopolymer it can containspacer non-cationic monomer units. Such polymers are described in theCTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of thecationic to non-cationic monomer units is selected to give polymershaving a cationic charge density in the required range, which isgenerally from 0.2 to 3.0 meq/gm. The cationic charge density of thepolymer is suitably determined via the Kjeldahl method as described inthe US Pharmacopoeia under chemical tests for nitrogen determination.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as (meth)acrylamide, alkyl anddialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone andvinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferablyhave C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Othersuitable spacers include vinyl esters, vinyl alcohol, maleic anhydride,propylene glycol and ethylene glycol.

The cationic amines can be primary, secondary or tertiary amines,depending upon the particular species and the pH of the composition. Ingeneral secondary and tertiary amines, especially tertiary, arepreferred.

Amine substituted vinyl monomers and amines can be polymerised in theamine form and then converted to ammonium by quaternization.

The cationic polymers can comprise mixtures of monomer units derivedfrom amine- and/or quaternary ammonium-substituted monomer and/orcompatible spacer monomers.

Suitable cationic polymers include, for example:

-   -   cationic diallyl quaternary ammonium-containing polymers        including, for example, dimethyldiallylammonium chloride        homopolymer and copolymers of acrylamide and        dimethyldiallylammonium chloride, referred to in the industry        (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;    -   mineral acid salts of amino-alkyl esters of homo- and        co-polymers of unsaturated carboxylic acids having from 3 to 5        carbon atoms, (as described in U.S. Pat. No. 4,009,256);    -   cationic polyacrylamides (as described in WO95/22311).

Other cationic polymers that can be used include cationic polysaccharidepolymers, such as cationic cellulose derivatives, cationic starchderivatives, and cationic guar gum derivatives.

Cationic polysaccharide polymers suitable for use in compositions foruse in the invention include monomers of the formula:

A-O[R—N⁺(R¹)(R²)(R³)X⁻],

wherein: A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual. R is an alkylene, oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹,R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms. The total number of carbon atoms for each cationic moiety(i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20or less, and X is an anionic counterion.

Another type of cationic cellulose includes the polymeric quaternaryammonium salts of hydroxyethyl cellulose reacted with lauryl dimethylammonium-substituted epoxide, referred to in the industry (CTFA) asPolyquaternium 24. These materials are available from the AmercholCorporation, for instance under the tradename Polymer LM-200. Othersuitable cationic polysaccharide polymers include quaternarynitrogen-containing cellulose ethers (e.g. as described in U.S. Pat. No.3,962,418), and copolymers of etherified cellulose and starch (e.g. asdescribed in U.S. Pat. No. 3,958,581).

A particularly suitable type of cationic polysaccharide polymer that canbe used is a cationic guar gum derivative, such as guarhydroxypropyltrimethylammonium chloride (commercially available fromRhodia in their JAGUAR trademark series). Examples of such materials areJAGUAR C135, JAGUAR C14, JAGUAR C15 and JAGUAR C17.

Mixtures of any of the above cationic polymers may be used.

Cationic polymer will generally be present in a shampoo composition foruse in the invention at levels of from 0.01 to 5%, preferably from 0.05to 1%, more preferably from 0.08 to 0.5% by total weight of cationicpolymer based on the total weight of the composition. Preferably anaqueous shampoo composition for use in the invention further comprises asuspending agent. Suitable suspending agents are selected frompolyacrylic acids, cross-linked polymers of acrylic acid, copolymers ofacrylic acid with a hydrophobic monomer, copolymers of carboxylicacid-containing monomers and acrylic esters, cross-linked copolymers ofacrylic acid and acrylate esters, heteropolysaccharide gums andcrystalline long chain acyl derivatives. The long chain acyl derivativeis desirably selected from ethylene glycol stearate, alkanolamides offatty acids having from 16 to 22 carbon atoms and mixtures thereof.Ethylene glycol distearate and polyethylene glycol 3 distearate arepreferred long chain acyl derivatives, since these impart pearlescenceto the composition. Polyacrylic acid is available commercially asCarbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acidcross-linked with a polyfunctional agent may also be used; they areavailable commercially as Carbopol 910, Carbopol 934, Carbopol 941 andCarbopol 980. An example of a suitable copolymer of a carboxylic acidcontaining monomer and acrylic acid esters is Carbopol 1342. AllCarbopol (trademark) materials are available from Goodrich.

Suitable cross-linked polymers of acrylic acid and acrylate esters arePemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum isxanthan gum, for example that available as Kelzan mu.

Mixtures of any of the above suspending agents may be used. Preferred isa mixture of cross-linked polymer of acrylic acid and crystalline longchain acyl derivative.

Suspending agent will generally be present in a shampoo composition foruse in the invention at levels of from 0.1 to 10%, preferably from 0.5to 6%, more preferably from 0.9 to 4% by total weight of suspendingagent based on the total weight of the composition.

Conditioners

Conditioner compositions will typically comprise one or more cationicconditioning surfactants which are cosmetically acceptable and suitablefor topical application to the hair.

Preferably, the cationic conditioning surfactants have the formulaN⁺(R¹)(R²)(R³)(R⁴), wherein R¹, R², R³ and R⁴ are independently (C₁ toC₃₀) alkyl or benzyl.

Preferably, one, two or three of R¹, R², R³ and R⁴ are independently (C₄to C₃₀) alkyl and the other R¹, R², R³ and R⁴ group or groups are(C₁-C₆) alkyl or benzyl.

More preferably, one or two of R¹, R², R³ and R⁴ are independently (C₆to C₃₀) alkyl and the other R¹, R², R³ and R⁴ groups are (C₁-C₆) alkylor benzyl groups. Optionally, the alkyl groups may comprise one or moreester (—OCO— or —COO—) and/or ether (—O—) linkages within the alkylchain. Alkyl groups may optionally be substituted with one or morehydroxyl groups. Alkyl groups may be straight chain or branched and, foralkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups maybe saturated or may contain one or more carbon-carbon double bonds(e.g., oleyl). Alkyl groups are optionally ethoxylated on the alkylchain with one or more ethyleneoxy groups.

Suitable cationic conditioning surfactants for use in conditionercompositions according to the invention include cetyltrimethylammoniumchloride, behenyltrimethylammonium chloride, cetylpyridinium chloride,tetramethylammonium chloride, tetraethylammonium chloride,octyltrimethylammonium chloride, dodecyltrimethylammonium chloride,hexadecyltrimethylammonium chloride, octyldimethylbenzylammoniumchloride, decyldimethylbenzylammonium chloride,stearyldimethylbenzylammonium chloride, didodecyldimethylammoniumchloride, dioctadecyldimethylammonium chloride, tallowtrimethylammoniumchloride, dihydrogenated tallow dimethyl ammonium chloride (e.g., Arquad2HT/75 from Akzo Nobel), cocotrimethylammonium chloride,PEG-2-oleammonium chloride and the corresponding hydroxides thereof.Further suitable cationic surfactants include those materials having theCTFA designations Quaternium-5, Quaternium-31 and Quaternium-18.Mixtures of any of the foregoing materials may also be suitable. Aparticularly useful cationic surfactant for use in conditionersaccording to the invention is cetyltrimethylammonium chloride, availablecommercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Anotherparticularly useful cationic surfactant for use in conditionersaccording to the invention is behenyltrimethylammonium chloride,available commercially, for example as GENAMIN KDMP, ex Clariant.

Another example of a class of suitable cationic conditioning surfactantsfor use in the invention, either alone or in admixture with one or moreother cationic conditioning surfactants, is a combination of (i) and(ii) below:

(i) an amidoamine corresponding to the general formula (I):

-   -   in which R¹ is a hydrocarbyl chain having 10 or more carbon        atoms,    -   R² and R³ are independently selected from hydrocarbyl chains of        from 1 to 10 carbon atoms, and    -   m is an integer from 1 to about 10; and

(ii) an acid.

As used herein, the term hydrocarbyl chain means an alkyl or alkenylchain.

Preferred amidoamine compounds are those corresponding to formula (I) inwhich

R¹ is a hydrocarbyl residue having from about 11 to about 24 carbonatoms,

R² and R³ are each independently hydrocarbyl residues, preferably alkylgroups, having from 1 to about 4 carbon atoms, and

m is an integer from 1 to about 4.

Preferably, R² and R³ are methyl or ethyl groups.

Preferably, m is 2 or 3, i.e. an ethylene or propylene group.

Preferred amidoamines useful herein includestearamido-propyldimethylamine, stearamidopropyldiethylamine,stearamidoethyldiethylamine, stearamidoethyldimethylamine,palmitamidopropyldimethylamine, palmitamidopropyldiethylamine,palmitamidoethyldiethylamine, palmitamidoethyldimethylamine,behenamidopropyldimethylamine, behenamidopropyldiethylmine,behenamidoethyldiethylamine, behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamidopropyldiethylamine,arachid-amidoethyldiethylamine, arachidamidoethyldimethylamine, andmixtures thereof.

Particularly preferred amidoamines useful herein arestearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixturesthereof.

Commercially available amidoamines useful herein include:

stearamidopropyldimethylamine with tradenames LEXAMINE S-13 availablefrom Inolex (Philadelphia Pa., USA) and AMIDOAMINE MSP available fromNikko (Tokyo, Japan), stearamidoethyldiethylamine with a tradenameAMIDOAMINE S available from Nikko, behenamidopropyldimethylamine with atradename INCROMINE BB available from Croda (North Humberside, England),and various amidoamines with tradenames SCHERCODINE series availablefrom Scher (Clifton N.J., USA).

Acid (ii) may be any organic or mineral acid which is capable ofprotonating the amidoamine in the hair treatment composition. Suitableacids useful herein include hydrochloric acid, acetic acid, tartaricacid, fumaric acid, lactic acid, malic acid, succinic acid, and mixturesthereof. Preferably, the acid is selected from the group consisting ofacetic acid, tartaric acid, hydrochloric acid, fumaric acid, andmixtures thereof.

The primary role of the acid is to protonate the amidoamine in the hairtreatment composition thus forming a tertiary amine salt (TAS) in situin the hair treatment composition. The TAS in effect is a non-permanentquaternary ammonium or pseudo-quaternary ammonium cationic surfactant.

Suitably, the acid is included in a sufficient amount to protonate allthe amidoamine present, i.e. at a level which is at least equimolar tothe amount of amidoamine present in the composition.

In conditioners for use in the invention, the level of cationicconditioning surfactant will generally range from 0.01 to 10%, morepreferably 0.05 to 7.5%, most preferably 0.1 to 5% by total weight ofcationic conditioning surfactant based on the total weight of thecomposition.

Conditioners for use in the invention will typically also incorporate afatty alcohol. The combined use of fatty alcohols and cationicsurfactants in conditioning compositions is believed to be especiallyadvantageous, because this leads to the formation of a lamellar phase,in which the cationic surfactant is dispersed.

Representative fatty alcohols comprise from 8 to 22 carbon atoms, morepreferably 16 to 22. Fatty alcohols are typically compounds containingstraight chain alkyl groups. Examples of suitable fatty alcohols includecetyl alcohol, stearyl alcohol and mixtures thereof. The use of thesematerials is also advantageous in that they contribute to the overallconditioning properties of compositions for use in the invention.

The level of fatty alcohol in conditioners for use in the invention willgenerally range from 0.01 to 10%, preferably from 0.1 to 8%, morepreferably from 0.2 to 7%, most preferably from 0.3 to 6% by weight ofthe composition. The weight ratio of cationic surfactant to fattyalcohol is suitably from 1:1 to 1:10, preferably from 1:1.5 to 1:8,optimally from 1:2 to 1:5. If the weight ratio of cationic surfactant tofatty alcohol is too high, this can lead to eye irritancy from thecomposition. If it is too low, it can make the hair feel squeaky forsome consumers.

Form of Composition

Compositions for use in the invention may suitably take the form of ahair oil, for pre-wash or post-wash use. Typically, hair oils willpredominantly comprise water-insoluble oily conditioning materials, suchas triglycerides, mineral oil and mixtures thereof.

Compositions for use in the invention may also take the form of a hairlotion, typically for use in between washes. Lotions are aqueousemulsions comprising water-insoluble oily conditioning materials.Suitable surfactants can also be included in lotions to improve theirstability to phase separation.

Hair treatment compositions according to the invention, particularlywater-based shampoos and hair conditioners, will preferably also containone or more silicone conditioning agents.

Particularly preferred silicone conditioning agents are siliconeemulsions such as those formed from silicones such aspolydiorganosiloxanes, in particular polydimethylsiloxanes which havethe CTFA designation dimethicone, polydimethyl siloxanes having hydroxylend groups which have the CTFA designation dimethiconol, andamino-functional polydimethyl siloxanes which have the CTFA designationamodimethicone.

The emulsion droplets may typically have a Sauter mean droplet diameter(D_(3,2)) in the composition for use in the invention ranging from 0.01to 20 micrometer, more preferably from 0.2 to 10 micrometer.

A suitable method for measuring the Sauter mean droplet diameter(D_(3,2)) is by laser light scattering using an instrument such as aMalvern Mastersizer.

Suitable silicone emulsions for use in compositions for use in theinvention are available from suppliers of silicones such as Dow Corningand GE Silicones. The use of such pre-formed silicone emulsions ispreferred for ease of processing and control of silicone particle size.Such pre-formed silicone emulsions will typically additionally comprisea suitable emulsifier such as an anionic or nonionic emulsifier, ormixture thereof, and may be prepared by a chemical emulsificationprocess such as emulsion polymerisation, or by mechanical emulsificationusing a high shear mixer. Pre-formed silicone emulsions having a Sautermean droplet diameter (D_(3,2)) of less than 0.15 micrometers aregenerally termed microemulsions.

Examples of suitable pre-formed silicone emulsions include emulsionsDC2-1766, DC2-1784, DC-1785, DC-1786, DC-1788 and microemulsionsDC2-1865 and DC2-1870, all available from Dow Corning. These are allemulsions/microemulsions of dimethiconol. Also suitable areamodimethicone emulsions such as DC2-8177 and DC939 (from Dow Corning)and SME253 (from GE Silicones).

Also suitable are silicone emulsions in which certain types of surfaceactive block copolymers of a high molecular weight have been blendedwith the silicone emulsion droplets, as described for example inWO03/094874. In such materials, the silicone emulsion droplets arepreferably formed from polydiorganosiloxanes such as those describedabove. One preferred form of the surface active block copolymer isaccording to the following formula:

HO(CH₂CH₂O)_(x)(CH(CH₃)CH₂O)_(y)(CH₂CH₂O)_(x)H

wherein the mean value of x is 4 or more and the mean value of y is 25or more.

Another preferred form of the surface active block copolymer isaccording to the following formula:

(HO(CH₂CH₂O)_(a)(CH(CH₃)CH₂O)_(b))₂—N—CH₂—CH₂—N((OCH₂CH(CH₃))_(b)(OCH₂CH₂)_(a)OH)₂

wherein the mean value of a is 2 or more and the mean value of b is 6 ormore.

Mixtures of any of the above described silicone emulsions may also beused.

The above described silicone emulsions will generally be present in acomposition for use in the invention at levels of from 0.05 to 10%,preferably 0.05 to 5%, more preferably from 0.5 to 2% by total weight ofsilicone based on the total weight of the composition.

Other Ingredients

A composition for use in the invention may contain other ingredients forenhancing performance and/or consumer acceptability. Such ingredientsinclude fragrance, dyes and pigments, pH adjusting agents, pearlescersor opacifiers, viscosity modifiers, and preservatives or antimicrobials.Each of these ingredients will be present in an amount effective toaccomplish its purpose. Generally these optional ingredients areincluded individually at a level of up to 5% by weight of the totalcomposition.

Hair treatment compositions for use in the invention are primarilyintended for topical application to the hair and/or scalp of a humansubject, either in rinse-off or leave-on compositions, for the treatmentof dry, damaged and/or unmanageable hair.

The invention will be further illustrated by the following, non-limitingExamples, in which all percentages quoted are by weight based on totalweight unless otherwise stated.

EXAMPLES

In the following examples, hair was treated, in accordance with theinvention, with shampoo and conditioner formulations comprising amixture of glucono delta lactone, sodium sulfate and trehalose, andcompared to a control formulations that did not comprise these actives.The treatment was carried out before exposure to ultraviolet light.

In the following examples, n=5.

Example 1: Composition of Shampoo Formulations 1 and A, and ofConditioner Formulations 2 and B

The shampoo formulations used in these examples are given in Table 1below. Shampoo 1 comprised glucono delta lactone, sodium sulfate andtrehalose.

Shampoo A did not comprise any of these fibre actives.

TABLE 1 Composition of shampoo formulations 1 and A. Amount in product(wt %, by total composition) 1 A Raw Material % Activity pH 4.4 pH 5.8Sodium Laureth Sulfate 70 17.14 17.14 Cocamidopropyl Betaine 30 5.335.33 Guar 100 0.25 0.25 Hydroxypropyltrimonium Chloride Dimethiconol 221.6 1.6 Glycerin 100 1 1 Disodium EDTA 100 0.05 0.05 Sodium Hydroxide 500.02 0.02 Glucono delta lactone 100 0.4 0 Sodium sulfate powder 100 0.10 Trehalose 100 0.1 0 Citric acid 50 1 1 Sodium chloride 100 1.3 1.3Water & minors — To 100 To 100 (fragrance, pigments, preservative) pH4.4 5.8

The conditioner formulations used in these examples are given in Table 2below. Conditioner 2 comprised glucono delta lactone, sodium sulfate andtrehalose. Conditioner B did not comprise any of these fibre actives.

TABLE 2 Composition of conditioner formulations 2 and B. Amount inproduct (wt %, by % total composition) Raw Material Activity 2 BStearamidopropyl 100 0.75 0.75 dimethylamine Cetearyl Alcohol 100 3 3Dimethicone and 100 1.429 1.429 Amodimethicone Lactic Acid 100 0.55 0.55Sodium Chloride 100 0.2 0.2 Trehalose 100 0.1 0 Sodium sulfate powder100 0.01 0 Glucono delta lactone 100 0.1 0 Behentrimonium 100 0.75 0.75Chloride Water & minors — To 100 To 100 (fragrance, pigments,preservative) pH 4.0 5.0

Example 2: Treatment of Hair with Shampoo Formulations 1 and A, andConditioner Formulations 2 and B

The hair used for these examples was 5 g, 10 inch mixed source darkbrown European tresses.

The hair tresses were washed with 14% SLES-1EO solution to remove anysurface contamination before starting any of the treatments. Each tresswas treated with 0.1 ml g⁻¹ hair of the SLES-1EO solution. Tresses werelathered for 30 s and then rinsed in warm water for 30 s. This treatmentwas repeated, after which the hair was detangled with a comb andair-dried.

Treatment Method

For shampoo treatments tresses were washed with 0.1 ml shampoo product(compositions I and A), per g hair. Tresses were lathered for 30 s andthen rinsed in warm water (35° C.-40° C.) for 30 s. This treatment wasrepeated, after which the hair was detangled with a comb.

For conditioner treatments tresses were treated with 0.2 g ofconditioner product (compositions 2 and B), per g hair. The product wasmassaged into towel-dried hair for 60 s and the rinsed in warm water for60 s. Treated tresses were detangled with a comb. Hair was left toair-dry.

Example 3: Infliction of Damage to Hair by Exposure to Ultraviolet Light

Hair was treated 20 times as described in Example 2 before each damageinfliction was applied.

Samples were taken at two time points:—

(1) (after an initial base wash) before any shampoo and conditionerwashes, and

(2) after the damage infliction.

The protocols for exposure to ultraviolet light was as follows:

An Atlas S3000 weatherometer set at 0.35 W/m2 (340 nm) giving anirradiance of 385 W/m2 in 300-800 nm, was used to expose the hairtresses to UV damage for 24 hours on each side, totalling 48 hours of UVexposure.

Example 4: Determination of Level of Damage by Differential ScanningCalorimetry DSC

In order to prepare hair samples for DSC, 2.54 cm of hair was cut fromthe tip-end of each tress. Hair was then chopped into 1-2 mm sections.

Measurements used a Mettler-Toledo DSC1 (with auto-sampler). 7-10 mgsamples of dry, finely chopped hair were placed in the tarred, basesections of 0.7 mm ‘Medium Pressure Stainless Steel DSC Pans’ andaccurately weighed on a 5 decimal place balance. 50 μL of deionisedwater was then added to each sample after which the pan lid (fitted witha rubber seal) was put on and the pans crimped shut to provide ahermetic seal. Pans were equilibrated for a minimum of 24 h ahead of anymeasurement to allow the hair to fully hydrate. The DSC was programmedto first heat each sample to 100° C. for 3 min and then to warm themfurther from 100 to 180° C. at a constant rate of 5° C. min⁻¹.

The results are given in Table 3 below.

TABLE 3 Change in denaturation temperature (ΔT_(denat)) upon bleachingor heat straightening in hair treated with shampoo and conditionercompositions 1 and 2, in accordance with the invention, or withcompositions A and B, as comparative examples. Protection TreatmentΔT_(denat) s.d. t-test (p value) Shampoo and Conditioner 2.25 0.490.00090 composition 1 and 2 Shampoo and Conditioner 0.73 0.24composition A and B

It will be seen that the denaturation temperature associated withultraviolet damage was significantly increased in the samples pretreatedwith shampoo and conditioner in accordance with the invention. This isevidence that the hair has been protected from protein damage.

1.-21. (canceled)
 22. A method of protecting hair, preferably theinternal protein of hair, from damage caused by ultraviolet light,comprising the step of applying, to the hair, a hair treatmentcomposition comprising a lactone, a disaccharide, an inorganic salt andan organic acid or salt thereof, having a pH in the range of from 3 to6.5, prior to the application of ultraviolet light to the hair. 23.Method as claimed in claim 22, wherein the step of applying, to thehair, a hair treatment composition comprising a lactone, a disaccharide,an inorganic salt and an organic acid or salt thereof, having a pH inthe range of from 3 to 6.5, is performed multiple times, preferably from2 to 50 times.
 24. Method as claimed in claim 22, wherein the damage iscaused by exposure to ultraviolet light multiple times.
 25. Method asclaimed in claim 22, wherein the hair treatment composition is a rinseoff hair treatment composition, preferably selected from a shampoo, aconditioner and a mask.
 26. Method as claimed in claim 25, in which theshampoo and the conditioner are used sequentially or a shampoo and masksequentially.
 27. Method as claimed in claim 25, in which the level oforganic acid, preferably lactic acid, in the conditioner or mask is from0.01 to 1 wt %.
 28. Method as claimed in claim 22, wherein the lactoneis a delta lactone selected from gluconolactone, galactonolactone,glucuronolactone, galacturonolactone, gulonolactone, ribonolactone,saccharic acid lactone, pantoyllactone, glucoheptonolactone,mannonolactone, galactoheptonolactone and mixtures thereof.
 29. Methodas claimed in claim 28, wherein the lactone is gluconolactone. 30.Method as claimed in claim 22, wherein the disaccharide comprises ofpentose or hexose sugars, more preferably the disaccharide comprises oftwo hexose units.
 31. Method as claimed in claim 30, wherein thedisaccharide is trehalose.
 32. Method as claimed in claim 22, whereinthe inorganic salt is sodium sulphate.
 33. Method as claimed in claim22, wherein the a hair treatment composition comprises a gluconolactone,trehalose, sodium sulphate and an organic acid or salt thereof, whereinthe pH of the composition is in the range of from 3 to 6.5, preferablyfrom 3 to 5 to protect the internal protein of hair from damage.